Detergent compositions with thermo controlled foaming capacity

ABSTRACT

FOAMING AT LOW WASHING TEMPERATURES IS OBTAINED WITHOUT OVERFOAMING AT HIGH TEMPERATURES. THE THERMO-CONTROLLER IS A SUBSTANCE OF THE GENERAL FORMULA   (H-R1-),(Z-OOC-R2-)-CYCLOHEXANE   IN WHICH R REPRESENTS A CARBON RING WITH, IF DESIRED, ONE OR MORE DOUBLE BONDS, WHICH MAY ALSO BE SEMICYCLIC; R1 AND R2 ARE CARBON CHAINS, AT LEAST ONE OF WHICH, PREFERABLY R2 IS BRANCHED, AND WHICH ARE SATURATED OR WHICH MAY CONTAIN ONE OR MORE DOUBLE BONDS, WHEREAS R1 AND R2 MAY ALSO BE ZERO. THE RING SYSTEM R MAY ALSO CARRY FURTHUR SUBSTITUENTS. Z IS A HYDROGEN ATOM OR A SALT-FORMING ELEMENT OR A SALT-FORMING GROUP.

May 16,1972

H. BA RTH El AL 3,663,446

DETERGENT COMPOSITIONS WITH THERMO CONTROLLED FOAMING CAPACITY Filed Feb. 19. 1968 70 I 8 0. 9b 750C Inventors:

Hans Barth, Wilhelm Griess, Martin Knuusenberger Henner Longe Hons-Udo Men: and Angelos Sugredos Their Attorney I U.S. or. 252-539 United States Patent 3,663,446 DETERGENT COMPOSITIONS WITH THERMO CONTROLLED FOAMING CAPACITY Hans Barth, Kleve, Wilhelm Griess, Mannheim-Almenhof, Martin Knausenberger, Hockenheim, Henner Lange, Hamburg, Hans-Udo Menz, Schenefeld-Hamburg, and Angelos Sagredos, Hamburg, Germany, assignors to Lever Brothers Company, New York, NY.

Filed Feb. 19, 1968, Ser. No. 706,445 Claims priority, application Germany, Feb. 24, 1967, U 13,590 Int. Cl. Clld 3/065 3 Claims ABSTRACT OF THE DISCLOSURE Foaming at low washing temperatures is obtained without overfoaming at high temperatures. The thermo-controller is a substance of the general formula in which R represents a carbon ring with, if desired, one or more double bonds, which may also be semicyclic; R and R are carbon chains, at least one of Which, preferably R is branched, and which are saturated or which may contain one or more double bonds, whereas R and R may also be zero. The ring system R may also carry further substituents. Z is a hydrogen atom or a salt-forming element or a salt-forming group.

Detergent compositions containing various active detergents, builders bleaching agents and optical brighteners are known. Efforts have been made to provide detergent compositions which are low-foaming at high temperatures, i.e. over about 90 0., but have acceptable foaming characteristics at temperatures of up to about 60 C. Such compositions would be very suitable for use in drum-type washing-machines, as over-foaming at higher temperatures would be avoided. It is known that this object can be attained to some extent if the formation of foam is suppressed by the addition of foam-reducing agents, such as liquid hydrocarbons or hydrocarbons that are solid at room temperature, e.g. parafiins or waxes. A drawback of these additives, however, is that they can adversely affect the detergency of the washing composition.

Foam suppression has also been obtained by incorporationg a proportion of soap in the detergent composition. Compositions where soap is employed for this purpose generally contain about l030% by weight of anionic detergent, such as alkyl benzene sulphonate, alkyl sulphate, fatty alcohol sulphate and the like, as well as polyphosphate in about the same up to a fivefold amount. Frequently also a certain amount of nonionic detergent is added; detergents of this kind may include the alkylene oxide condensation products of alkyl alcohols, of alkylphenol, of polyoxypropylene, of fatty acid amide, and of other organic hydrophobic compounds. Detergent compositions of this type, the so-called mixed-active detergent compositions, further usually contain an oxygen-liberating bleaching agent, such as perborate, silicate and small quantities of optical brighteners and soil-suspending agents, such as carboxy methyl cellulose.

It is known that the foam-suppressing action provided by the soap component in such detergent compositions is stronger at higher temperatures than at lower temperatures if the soap has a relatively high content of saturated molecules with at least 20 carbon atoms. However, these soaps still give a distinct suppression of foam at low and medium temperatures, which in many respects is undesirable.

It has now surprisingly been found that the adjustment of the foaming capacity of such mixed-active detergent compositions at different temperatures can be achieved far better and far more accurately as compared with conventional methods if the soap constituent of the detergent composition is wholly or partly replaced by substances of the general formula RzCOOzZ ther substituents. Z is a hydrogen atom or a salt-forming element or a salt-forming group.

Foam control agents similar to the substances of the above general formula but differing in that R and R are straight chain rather than branched chain, as in the present application, are described in application Ser. No. 669,845, zfiled Sept. 22, 1967, now abandoned.

The two side chains indicated above are preferably in 1,2-position to each other.

The number of carbon atoms inchain R may appropriately range from 0 to 1 6, preferably from 0 to 12, and that in chain R from 2 to 21, the total number of carbon atoms in both chains R and R ranging from 5 to 33, preferably from 10 to 20.

Favourable results are obtained by using acids, their salts and/or mixtures which contain at least 12 carbon atoms and not more than. 24 carbon atoms in the molecule, corresponding with a sum of R +R of between 5-17. Very suitable compounds have 18 carbon atoms in the molecule, corresponding with a total number of carbon atoms in chains R and R of 11.

In particular those mixtures are preferred that contain not more than 10% by weight, advantageously less than 5% by weight, of constituents in which R; is zero.

Suitable branched compounds are those in which the branching in the carbon chain is not on the carbon atom directly connected to the ring, or if so, those having a cumene-like side chain structure of which the aliphatic chains comprise no further branching.

The cyclic compounds according to the above formula or their mixtures may be obtained in a known way by the Friedel-Crafts alkylation of benzene or alkylbenzene with unsaturated fatty acids in the presence of suitable catalysts. The fatty acids used should have 3 to 22 carbon atoms and at least one double bond. Useful catalysts are the Friedel-Crafts catalysts such as aluminium chloride, boron fluoride, etc.

The following illustrates such a cyclic acid production:

(A) In a three-litre round-bottomed flask provided with stirrer, reflux condenser, thermometer and dropping funnel, 584 g. (approx. 2.1 moles) oleic acid was added dropwise for 45 minutes at room temperature to a mixture of 1104 g. (12 moles) toluene and 320 g. (2.4 moles) aluminium chloride, whereby the temperature gradually rose to about 40 C. Subsequently the reaction mixture was heated with continuous agitation for 4 hours to 80 C., after which it was added to three times its volume of hydrochloride acid. After about 15 hours the oil phase was separated, freed of the mineral acids by washing with water, and dried. After the excess of toluene had been distilled off (at atmospheric pressure) the crude reaction product was subjected to fractional distillation under vacuum whereby the main part of methyl phenyl stearic acid distilled over between 240255 C. Yield: 395 g., i.e. about 51% of the theoretical amount.

The distillate was identified as a mixture of isomeric methyl phenyl stearic acids by analytical measurements made with the aid of gas chromatography, mass spectrometry and U.V.- and I.R.-spectroscopy.

(B) In a threee-litre round-bottomed flask provided with stirrer, reflux condenser, thermometer and feeed pipe, BF (290 g.) was introduced into a mixture of 1818 g. (approx. moles) toluene and 904 g. (4.9 moles) undecylenic acid at 80 C. for 2 /2 hours with stirring until the saturation point was reached. The reaction product was poured into ice water, extracted with diethyl ether and washed with water until the reaction was neutral (indicator methyl orange). After the diethyl ether and the excess of toluene had been distilled off, the reaction product was subjected to fractional distillation under vacuum, whereby the main part of methyl phenyl undecanoic acid distilled over between 192205 C. Yield: 51.6% of the theoretical amount.

The distillate was identified as a mixture of isomeric methyl phenyl undecanoic acids by analytical measurements.

250 g. methyl phenyl undecanoic acid were subjected to catalytic hydrogenation in glacial acetic acid in the presence of 1.25 g. PtO in a one-litre autoclave at 180 200 C. and up to about 170 atm. for 13 hours. The hydrogenated product was filtered off from the catalyst, freed of the acetic acid by washing out, and finally distilled under vacuum, whereby the main part of methyl cyclohexyl undecanoic acid (approx. 230 g.) distilled over between l80-192 C.

The distillate was established to be a mixture of isomeric methyl cyclohexyl undecanoic acids by analytical measurements.

(C) 282 g. (1 mole) of oleic acid was introduced dropwise and with constant stirring into a mixture of 720 g. (6 moles) cumene and 160 (1.2 moles) aluminium chloride in the course of about 15 min. The reaction mixture was subsequently heated with continuous stirring to 70 C. for 4 hours and worked up in the way described in Process A. The crude product was subjected to fractional distillation under vacuum, whereby the main part of isopropyl phenyl stearic acid distilled over between 231- 255 C. Yield: 194 g., i.e. 48% of the theoretical amount.

According to the analytical measurements the distillate consisted of a mixture of isomeric isopropyl phenyl stearic acids.

Subsequently, the products thus obtained may or may not be subjected to total or partial hydrogenation.

The cyclic compounds used as detergent components according to the invention not only show the advantage, as was surprisingly found, of having a good foaming capacity at low temperatures and an effective foam suppression at elevated temperatures, but moreover they are excellent detergents, which are at least equal to the soaps usually incorporated in detergent compositions.

The foam-suppressing action at elevated temperatures provided by the cyclic substances used according to the invention is so good that in most cases the desired foamsuppressing at elevated temperatures can be achieved by substituting the substances of the invention for only part of the soap portion normally contained in such detergent compositions.

In many cases it is advisable to replace only part of the soap portion of the detergent composition by the substances according to the invention because their foaming capacity at low and medium temperatures, i.e. at temperatures up to about 60 C., is so much superior to that of the long-chain fatty acids that a detergent composition in which the soap component is entirely replaced by the substances of the invention would produce too much foam in the low temperature range, in spite of the practically complete suppression of foam at elevated temperatures. The cyclic acids or their salts according to the invention are therefore preferably introduced into these detergent compositions in such an amount that the soap component is replaced by the cyclic acids or their salts for 20-70%, in particular for about 45-55%.

For practical purposes it suffices to use the acid mixture obtained from the cyclisation process of fatty acids, without previously isolating it from the non-cyclic constituents.

Detergent compositions according to the invention may contain the usual additives, such as optical brighteners or other colorants, perborate stabilizers, perfume, etc.

The use according to the invention of the cyclic carboxylic acids and their salts is not restricted to the washing of laundry, but they may also be advantageously applied in any other cleaning process in which it is desired that at elevated temperatures less foam is produced than in the low and medium temperature ranges.

In the following examples various detergent compositions according to the invention are given. Their foaming behaviour under dynamic conditions was determined in a rotary foaming apparatus, analogous to that described by H. Bloching, W. Fries and H. I. Heitland in Seifen, Ole, Fette, Wachse, 91, 25, 1965, page 1913, using the following test conditions:

water =15 German hardness soil load=2.8 g./l. detergent concentration=7 g./l.

The results are shown in the accompanying graph wherein the horizontal axis represents temperature and the vertical axis indicates the percentage of the total cylinder height, taken as the unit of measure for the height of lather generated in the apparatus at a given temperature.

EXAMPLE 1 Percent Sodium alkyl benzene sulphonate 11 C -C fatty alcohol polyglycol ether 4 Sodium salt of cyclohexyl undecanoic acid 3 Sodium tripolyphosphate 40 Sodium perborate 22 Sodium silicate 5 Sodium carboxy methyl cellulose 1 Water and residual salts 14 cH2)m' COOH CQHH CH H2) 6- 1 m'+n=8.

EXAMPLE 2 Percent Sodium alkyl benzene sulphonate 11 Cgo-Czz fatty alcohol polyglycol ether 4 Sodium salt of phenyl undecanoic acid 3 Sodium tripolyphosphate 40 Sodium perborate 22 Sodium silicate 5 Sodium carboxy methyl cellulose 1 Water and residual salts 14 cm ...-ooon C ll -CH 0H?) ..--CH, m+n=8.

EXAMPLE 3 Percent Sodium alkyl benzene sulphonate 11 C -C fatty alcohol polyglycol ether 4 Sodium salt of toluyl undecanoic acid 3 Sodium tripolyphosphate 40 Sodium perborate 22 Sodium silicate 5 Sodium carboxy methyl cellulose 1 Water and residual salts 14 (OH2)m-C O OH CH3C6H4--CH CH2) nOH m+n=8.

EXAMPLE 4 Percent Sodium alkyl benzene sulphonate 11 C C fatty alcohol polyglycol ether 4 Isopropyl phenyl stearic acid 3 Sodium tripolyphosphate 40 Sodium perborate 22 Sodium silicate 5 Sodium carboxy methyl cellulose 1 Water and residual salts 14 CH; CHzh-COOH \CH-COH4'CH CH3 (CH2)n CH3 m+n=15.

What is claimed is:

1. Detergent compositions consisting essentially of from about to about 30% by weight of alkyl benzene sulphonate, and 1 to about 5 times of said amount of a polyphosphate builder, in which there is incorporated as a foam-controlling agent, a material selected from the group consisting of cyclic acids and sodium salts of such acids, said acids being a mixture of isomers having the formula:

RZCOOH wherein R is either a cyclohexyl or a benzene radical; R is an aliphatic hydrocarbon chain having from 0-16 carbon atoms, R; is a branched aliphatic hydrocarbon chain having from 2-21 carbon atoms; the total number of carbon atoms of R and R being from 5-33, wherein said foam-controlling agent is present in an amount effective to cause foam suppression of the detergent composition at high temperatures.

2. Detergent compositions according to claim 1 in which there is incorporated as a foam-controlling agent a material selected from the group consisting of cyclic acids and sodium salts of such acids, said acids being a mixture of isomers having the formula:

RzCOOH wherein R is either a cyclohexyl or a benzene radical; R and R are aliphatic hydrocarbon chains having a total number of carbon atoms of about between 10 and 20.

3. Detergent compositions according to claim 1, in which said cyclic acids are present in an amount not exceeding the amount of alkylbenzenesulphonate detergent, wherein said foam-controlling agent is present in an amount effective to cause fioam suppression of the detergent composition at high temperatures.

References Cited UNITED STATES PATENTS LEON D. ROSD OL, Primary Examiner P. E. WILLIS, Assistant Examiner US. Cl. X.R. 252-121, 558 

